Surfactants are used to assist the zero-valent iron-mediated reductive dechlorination (ZVI-RD) of hydrophobic organic contaminants (HOCs). Although the effect of surfactants has been investigated in single-factor systems, the relationships between the surfactant and the matrix properties during RD are not well understood. Thus, an orthogonal experiment and post-experiment characterization of ZVI were conducted in the present study to estimate the integrated effects of plausible factors. The results showed that the introduction of surfactants significantly influenced the reduction of 2,2′,5,5′-tetrachlorinated biphenyl (PCB-52) by altering the contact between ZVI and PCB-52. An anionic surfactant was able to alleviate the adverse impact of high amounts of non-ionic surfactants and humic acid (used as representative soil organic matter) by changing their sorption behaviors, which were also influenced by the initial pH value. However, the reduction of ZVI by humic acid decreased the electron transfer efficiency of ZVI, and also reduced the contact between ZVI and PCB-52 by generating FeCO3. These results suggest that the rate-limiting process for the ZVI-RD of HOCs in the soil/sediment solution is the contact between ZVI and HOCs, which can be improved by the addition of surfactants at concentrations corresponding to the maximum adsorption capacity of HOCs on the ZVI surface